Abstract:

Claims:

1. A copolyesteramide polymer of formula (I): ##STR00009## whereinR at
each occurrence is independently an aliphatic group, a heteroaliphatic
group, cycloalkylene (preferably C3-C7 cycloalkylene),
-alkylene-cycloalkyl-, -alkylene-cycloalkyl-alkylene-,
-heteroalkylene-cycloalkyl-, -cycloalkyl-heteroalkylene-,
-heteroalkylene-cycloalkyl-heteroalkylene-, or a polyalkylene oxide;R'
and R'' at each occurrence are independently a bond or an aliphatic
group, cycloalkylene, -alkylene-cycloalkyl-, or
-alkylene-cycloalkyl-alkylene-;RN is --N(R2)--Ra--N(R2)--
where R2 is independently H or C1-C6 alkyl, Ra
independently is a heterocycloalkylene group, an aliphatic group,
cycloalkylene, -alkylene-cycloalkyl-, -cycloalkyl-alkylene-, or
-alkylene-cycloalkyl-alkylene, wherein the heterocycloalkylene group
contains two nitrogen atoms connecting the heterocycloalkylene to the
adjacent carbonyl groups;x is an integer of 0 or higher that represents
the number of ester units and y is an integer of 2 or higher that
represents the number of amide units in the copolymer;each n
independently represents an integer of 1 or greater; andwherein the
copolymer of formula (I) comprises two or more said amide units:where n
is 1 in at least half the number of said amide units; andwherein n is
greater than 1 in at least one of said amide units,with the copolymer
having an Hw of greater than 1.05 and less than 1.9, wherein Hw is a
weighted average value of n.

2. A polymer according to claim 1 wherein x is 1 or higher.

3. A polymer according to claim 1 wherein R at each occurrence is
independently C2-C12 alkylene.

7. A polymer according to claim 1 wherein R' and R'' at each occurrence
are C2-C10 alkylene.

8. A polymer according to claim 1 wherein RN is --N(H)--Ra--N(H)--
and Ra is C2-C12 alkylene.

9. A polymer according to claim 1 wherein RN is piperazin-1,4-diyl.

10. A polymer according to claim 2, wherein there are two or more
occurrences of R' or R'' and in at least two of the two or more
occurrences, the R' or R'' are different.

11. A process for making a copolyesteramide polymer according to claim 1,
the process comprising:(a) providing a monomer product comprising a
mixture of two or more monomers of formula (A): ##STR00010## wherein
RB is independently at each occurrence H or C1-C6
alkyl,and wherein each n independently is an integer of 1 or higher and n
is 1 in at least half of the monomers and n is greater than 1 in at least
one of the monomers,with the monomer product having an Hw, of
greater than 1.05 and less than 1.9, wherein Hw is a weighted
average value of n;(b) copolymerizing the monomers of formula (A) with a
diacid or diester of formula
(C):RBO--OC(═O)--R'--C(═O)ORB (formula (C))and one or
more diols of formula (D):HO--R--OH (formula (D)),to provide the polymer
of formula (I).

12. A process according to claim 11 wherein the monomer product of formula
(A) is prepared by reacting a diamine of formula (B):H--RN--H
(formula (B))with a diacid or diester of formula
(C):RBO--OC(═O)--R''--C(═O)ORB (formula (C)).

13. A process according to claim 11 wherein the one or more diols is a
mixture of diols.

14. A process according to claim 13 wherein the mixture of diols is
1,4-butanediol and an isomer mixture of 1,3- and
1,4-cyclohexanedimethanol.

15. A process according to claim 13 wherein the mixture of diols is
1,4-butanediol and polytetramethylene ether glycol.

16. A process according to claim 11 wherein the polymer of formula (I) is
prepared by in-situ synthesis.

17. A process according to claim 11 wherein the polymer of formula (I) is
prepared by a one-pot process.

18. A copolymer prepared by the process of claim 11.

Description:

[0002]Polyesteramides, materials in which amide functionalities are
incorporated into polyesters, have attracted strong industrial interest
primarily because of their excellent heat resistance properties, their
amenability to processing, and their potential for biodegradability.
Various methods have been described in the prior art for the preparation
of polyesteramides. One such method involves reaction of a diamine with a
dicarboxylic acid or ester to form a diester diamide. The diamide diester
is isolated and purified, and then further reacted with a diol and a
diester to form the polymer.

[0003]The known processes for preparing polyesteramides are, in general,
complex and uneconomical, especially in view of the several synthetic,
isolation, and purification steps required to achieve final polymer.
Consequently, a need exists for simpler and more economical processes for
preparing polyesteramides. A need also exists for new polyesteramides
that exhibit improved physical properties compared to known systems.

BRIEF SUMMARY OF THE INVENTION

[0004]In one aspect, the invention provides a copolyesteramide of formula
(I):

##STR00001##

[0005]wherein [0006]R at each occurrence is independently an aliphatic
group (preferably C2-C12 alkylene), a heteroaliphatic group
(preferably heteroalkylene of about 2 to about 12 backbone atoms),
cycloalkylene (preferably C3-C7 cycloalkylene),
-alkylene-cycloalkyl-, -alkylene-cycloalkyl-alkylene-,
-heteroalkylene-cycloalkyl-, -heteroalkylene-cycloalkyl-heteroalkylene-,
or polyalkylene oxide [such as polytetramethylene ether (i.e. R is
--CH2CH2CH2CH2--(OCH2CH2CH2CH2).s-
ub.m--), polypropylene oxide (i.e. R is
--CH2CH(CH3)--[OCH2CH(CH3)]m--), or polyethylene
oxide (i.e. R is --CH2CH2--(OCH2CH2)m--),
wherein each m independently is an integer of 1 or higher]; [0007]R' and
R'' at each occurrence are independently a bond or an aliphatic group
(preferably of 1 to 10, more preferably 2-6 carbon atoms), cycloalkylene
(preferably C3-C7 cycloalkylene), -alkylene-cycloalkyl-, or
-alkylene-cycloalkyl-alkylene-; [0008]RN is
--N(R2)--Ra--N(R2)--, where R2 is independently H or
C1-C6 alkyl (preferably both H), Ra independently is a
heterocycloalkylene group, an aliphatic group (preferably alkylene group
of 2 to 12, preferably 2-6 carbon atoms), cycloalkylene (preferably
C3-C7 cycloalkylene), -alkylene-cycloalkyl-, or
-alkylene-cycloalkyl-alkylene, wherein the heterocycloalkylene group
contains two nitrogen atoms connecting the heterocycloalkylene to the
adjacent carbonyl groups (e.g., RN is piperazin-1,4-diyl); [0009]x
is an integer of 0 or higher that represents the number of ester units
and y is an integer of 2 or higher that represents the number of amide
units in the copolymer; [0010]each n independently represents an integer
of 1 or greater; and [0011]wherein the copolymer of formula (I) comprises
two or more said amide units: [0012]where n is 1 in at least half the
number of said amide units; and [0013]wherein n is greater than 1 in at
least one of said amide units, [0014]with the copolymer having a weighted
average value of n, represented herein by Hw, of greater than 1.05
and less than 1.9. Preferably, x is 1 or higher.

[0015]In another aspect, the invention provides a process for making a
polyesteramide copolymer of formula (I), the process comprising:
[0016](a) providing a monomer product comprising a mixture of two or more
monomers of formula (A):

##STR00002## wherein each n independently represents an integer of 1
or higher and n is 1 in at least half of the monomers and n is greater
than 1 in at least one of the monomers, with the monomer product having
an Hw, of greater than 1.05 and less than 1.9, wherein Hw is a
weighted average value of n and RN and R'' are as defined above,
RB is independently at each occurrence H or C1-C6 alkyl;

[0017](b) copolymerizing the monomers of formula (A) with at least one
diacid or diester of formula (C):

[0017]RBO--OC(═O)--R'--C(═O)ORB (formula (C))
wherein RB and R' are as defined above, and at least one diol of
formula (D):

HO--R--OH (formula (D)) wherein R is as defined above, to provide the
polymer of formula (I).

[0018]In a further aspect, the invention provides polymers of formula (I)
prepared according to the processes described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019]FIG. 1 is a DSC of various polyesteramide polymers prepared using
different types of monomer feed.

[0020]FIG. 2 is a cool from melt DSC various polyesteramide polymers
prepared using different types of monomer feed.

[0021]FIG. 3 shows tensile properties of various polyesteramide polymers
prepared using different types of monomer feed.

[0023]In one aspect, the invention provides a polyesteramide copolymer of
formula (I):

##STR00003##

[0024]wherein [0025]R, R', R'', RN, n, x, and y are as defined
above with the copolymer having a weighted average value of n,
represented herein by Hw, of greater than 1.05 and less than 1.9. In
another aspect, the invention provides a copolyesteramide of formula (I)
as defined above wherein x is 1 or higher.

[0026]While for convenience the repeat units of the copolymers of the
invention are as shown, the copolymers are not necessarily block
copolymers. Rather, the invention encompasses all possible distributions
of the x and y units in the copolymers, including randomly distributed x
and y units, alternately distributed x and y units, as well as partially
and fully block or segmented copolymers.

[0027]Further, although again for convenience only one x unit and only y
unit is represented for each copolymer, it should be noted that even
though each individual defined group (e.g., each R group) may be the same
throughout a specific x or y unit, the invention also encompasses
materials where a defined group differs from one x unit to another x unit
(or one y unit to another y unit) in the same copolymer. Thus, for
example, the invention encompasses a copolymer prepared from two or more
different amide monomers such as monomers based on ethylene diamine and
diaminohexane, two or more different diesters, two or more different
diols, etc. (syntheses are discussed more fully below).

[0028]Preferred polymers of formula (I) include polymers wherein R at each
occurrence is the same and is an aliphatic group. More preferably, R is
C2-C6 alkylene, and even more preferably it is
--(CH2)4--.

[0029]Preferred polymers of formula (I) also include polymers wherein R is
heteroaliphatic, cycloalkylene (preferably C3-C2
cycloalkylene), -alkylene-cycloalkyl-alkylene-,
-heteroalkylene-cycloalkyl-, or
-heteroalkylene-cycloalkyl-heteroalkylene-. Preferred
-alkylene-cycloalkyl-alkylene- for this embodiment includes dimethylene
cyclohexyl. Preferred heteroalkylene groups for this embodiment include
oxydialkylenes such as diethylene glycol
(--CH2CH2OCH2CH2--).

[0030]Preferred polymers of formula (I) further include polymers where R
is a polyalkylene oxide, i.e., R together with the oxygens to which it is
attached forms a bridging polyol, such as polytetramethylene ether,
polypropylene oxide, polyethylene oxide, other polyalkylene oxides,
including polyalkylene oxides containing mixed length alkylenes.

[0031]Preferred polymers of formula (I) also include polymers wherein R'
at each occurrence is the same and is an aliphatic group. More
preferably, R' is C1-C6 alkylene, and even more preferably it
is --(CH2)4--.

[0032]Preferred polymers of formula (I) also include polymers wherein R''
at each occurrence is the same and is an aliphatic group. More
preferably, R'' is C1-C6 alkylene, and even more preferably it
is --(CH2)4--.

[0033]Preferred polymers of formula (I) also include polymers wherein
there are two or more occurrences of R' or R'' and in at least two of the
two or more occurrences, the R' or R'' are different.

[0034]Preferred polymers of formula (I) also include polymers where
RN is --N(R2)--Ra-- N(R2)--. Preferably, both R2
groups are hydrogen. Also preferably, Ra is alkylene, and particularly,
ethylene, butylene, or hexylene. Most preferred Ra groups are ethylene
and hexylene (--(CH2)6--).

[0035]In the invention, Hw of the formula (I) polymer is greater than
1.05, preferably at least 1.06, more preferably at least 1.07, even more
preferably at least 1.08, and further preferably at least 1.09. In a
further preferred embodiment, Hw is at least 1.1. In additional
embodiments, Hw is at least 1.3, at least 1.5, or at least 1.7.
Hw in the invention is less than 1.9.

[0036]The copolymer of formula (I) comprises two or more y units where n
is 1 in at least one y unit; and wherein n is greater than 1 in a least
one y unit. In the invention, such a polymer is referred to as having
"decreased perfection" of the amide sequence. The terms "y unit" and
"amide unit" are used interchangeably herein. Referring to numbers of the
y units (i.e., amide units) relative to each other, preferably the
polymer contains predominantly (i.e., greater than 50 mole percent) n=1 y
units (i.e., more than half the total number of amide units are n=1 amide
units), but also contains additional longer amide sequence y units (i.e.,
amide units wherein n is 2 or higher) such that less than 50 mole percent
of y units (i.e., less than half the total number of amide units) are
those where n is 2 or higher.

[0037]In further embodiments, it is also preferred that the y units in the
polymer of formula (I) contain at least about 60 mole percent where n=1
in the y units, more preferably at least about 70 mole percent, even more
preferably at least about 85 mole percent. It is further preferred that
the polymer contain no more than 95 mole percent n=1 in the y units (with
the remainder being higher sequence amides, such n=2, n=3, and/or n=4,
etc.).

[0038]The inventors have discovered that the decreased perfection polymers
of formula (I) surprisingly provide improved physical properties as
demonstrated by the Examples below, including improved thermal stability
when compared to material which is essentially completely n=1 polymer. As
shown by the Examples, such improved properties also include increased
melting range (related to the aforementioned thermal stability), melting
onset, melting completion, crystallization temperature, and
crystallization onset. Examples of other useful properties of the
decreased perfection polymers of formula (I) are tensile strength,
modulus, and percent elongation to break. Another particularly useful
property of the decreased perfection polymers of formula (I) is earlier
(e.g., immediate after initiation of plastic deformation) onset of strain
hardening under tensile strain (see FIG. 3).

[0039]Such properties show that the decreased perfection polymers of
formula (I) are useful in foams, films, coatings, hot melt adhesives,
fibers, fabrics, and extruded and molded articles, which comprise
additional aspects of the present invention.

[0040]In another aspect, the invention provides a process for preparing
polymers of formula (I). The process comprises: [0041](a) providing a
monomer product comprising a mixture of two or more monomers of formula
(A):

##STR00004## wherein RB is independently at each occurrence H or
C1-C6 alkyl; each n independently represents an integer of 1 or
higher and n is 1 in at least half of the monomers and n is greater than
1 in at least one of the monomers, with the monomer product having an
Hw of greater than 1.05 and less than 1.9, wherein Hw is a
weighted average value of n, and RN and R'' are as defined above for
formula (I);

[0042](b) copolymerizing the monomers of formula (A) with at least one
diacid or diester of formula (C):

[0042]RBO--OC(═O)--R'--C(═O)ORB (formula (C)),
wherein R' is as defined above for formula (I); and at least one diol of
formula (D):

HO--R--OH (formula (D)), wherein R is as defined above for formula
(I), to provide the polymer of formula (I).

[0043]The monomer product comprising a mixture of two or more monomers of
formula (A) (also referred to herein as decreased perfection monomers) is
an unpurified mixture of monomers containing at least half of, preferably
predominantly, monomer where n is 1, but also other monomer(s) where n is
greater than one. Monomers where n is greater than one are referred to
herein as high or higher sequence monomers. In addition, to providing
polymers with advantageous properties, as discussed above and illustrated
by the Examples, the use of unpurified monomers also reduces the steps
required to prepare the polymers, thereby reducing costs as well as the
environmental impact of the polymerization process, in part because of
the decreased need for raw materials that would normally be required to
purify the monomer.

[0044]Various analytical methods can be used to assess the level of
decreased perfection in the polymer of formula (I) with a convenient
method being nuclear magnetic resonance (NMR) spectroscopy (as
illustrated below). Using NMR spectroscopy, resonances from atoms in the
amide unit of the polymer (i.e., the unit quantified by n) can be
integrated against resonances from atoms outside the amide unit but
inside the y unit (i.e., the unit of the polymer quantified by "y") to
determine a weighted number of amide units in the y unit, referred to
herein as Hw.Hw=Σnimi/Σmi where
ni is the integer number for each n and mi is the moles or mole
fraction for each n.

[0045]Thus, for instance, if the polymer is completely n=1 polymer, then
Hw would be 1. When Hw is greater than 1, the polymer contains
y units with higher amide sequences (e.g., n=2 and/or n=3, etc.). By way
of further example, if a material is 95 mol % n=1 and 5 mol % n=2, then
Hw is 1.05 (i.e., (0.95×1)+(0.05×2)). If a material is
95 mol % n=1, 4% n=2, and 1% n=3, Hw for the polymer is 1.06. If a
material is 6 moles n=1, 3 moles n=2, and 1 mole n=3, Hw=1.5.

[0046]Using NMR to determine Hw for a polymer is within the skill of
a person of ordinary skill in the art as long as the key atom resonances
are readily distinguishable in an NMR spectrum. With Hw being
essentially the same in an amide monomer and the polymer prepared from
that amide monomer under normal polymerization conditions, it is usually
simpler to measure Hw from the NMR spectrum of the amide monomer
used to form the polymer of formula (I) since there are no atom resonance
contributions from the ester portion, x, of the polymer of formula (I) to
complicate the spectra. Determining Hw based on the monomer is also
preferable as NMR peaks from the monomer tend to be narrower, and
therefore more readily distinguishable than in the polymer.

[0047]The purity and Hw value for a monomer product of formula (A)
can be readily assessed using proton NMR, in the same manner as described
above for polymers. Particularly useful NMR resonances for the monomer
are the signals from the protons of the terminal acid or alkyl ester (the
RB group protons) and the signals from the protons most adjacent to
the amide nitrogen (for example, if RN in formula (A) is
--N(H)--(CH2)4--N(H)--, then the resonance from the methylenes
directly adjacent to the amide nitrogen are preferably used). As will be
readily understood, one skilled in the art can use other resonances in
NMR, as well as other types of NMR such as carbon NMR, to assess monomer
purity, or can use other techniques entirely. The technique used to
measure purity is not critical to the invention.

[0048]By way of illustration, for a monomer of the following formula
(designated A4A in the examples below):

##STR00005##

Hw can be determined using 1H NMR by integrating a methylene
adjacent to an amide nitrogen (chemical shift of about 3.3-3.4 ppm) and
the signal from a terminal methoxy (chemical shift of about 3.6-3.7 ppm).
As seen in the Examples below, the signals integrate to 0.775 for the
methylene protons and 1 for the methoxy protons (for crude A4A monomer).
So for this specific A4A molecule, OCH3/CH2N=6/(4Hw)=1/0.775, so
solving for Hw, Hw is 1.1625. With changes in the type of ester
(or even carboxylic acid) or the type of amine used to make amide or
selection of other atom resonances Hw can be readily determined, but
the above formula might need adjustments to calculate Hw, which one
of ordinary skill in the art can do.

[0049]In the invention, Hw of the formula (A) monomer product is
greater than 1.05, preferably at least 1.06, more preferably at least
1.07, and even more preferably at least 1.08. In a further preferred
embodiment, Hw is at least 1.1. In additional embodiments, Hw
is at least 1.2, at least 1.3, at least 1.5, or at least 1.7. Hw in
the invention is less than 1.9. Monomers having Hw of greater than
1.05 are referred to herein as "crude" monomers. Monomers having Hw
of 1.05 or less are referred to herein as "pure" monomers.

[0050]In further embodiments, it is also preferred that the monomer
product of formula (A) contain at least about 60 mole percent n=1
monomer, more preferably at least about 70 mole percent, even more
preferably at least about 85 mole percent. It is further preferred that
the monomer product contain no more than 95 mole % n=1 monomer (with the
remainder being higher sequence amides, such as n=2, n=3, and/or n=4,
etc.).

[0051]Monomers of formula (A) can be readily prepared by those skilled in
the art using well known methods. The purity of the monomer product is
influenced by a variety of factors, including the reaction conditions,
the conditions used for the isolation and/or purification of the monomer,
as well as the solubility characteristics of the monomer. In addition,
the ratio of diester to diamine can impact the product distribution in
the monomer, the amount of longer amide sequences (n=2, 3, 4, etc in
formula (A)). For instance, at infinite dilution of diamine by diester,
reaction should lead to essentially pure n=1 monomer, but for a ratio
such as 10 moles of diester to 1 mole of diamine, the reaction results in
predominantly n=1 monomer but with increasing amounts of longer amide
sequence monomers such as n=2 monomer, and/or n=3, etc.

[0052]In a typical procedure for preparing the monomer of formula (A), a
diamine, such as that of formula (B) below, is reacted with an excess
(e.g., 3 to 15 mole excess) of a dicarboxylic acid or ester of formula
(C) under an inert atmosphere.

H--RN--H formula (B)

RBO--OC(═O)--R''--C(═O)ORB formula (C)

[0053]The reaction is carried out neat or in the presence of a catalyst
such as titanium (IV) butoxide. The selection of catalyst and the amount
of catalyst preparing amides from amines and carboxylic acids or esters,
in general, is known and selected by one skilled in the art. The
temperature of the reaction mixture is preferably slowly raised up to
about 100° C., and the reaction continued until a desired quantity
of product is formed, for instance about 12 hours. Depending on a
particular diamine, temperature of the reaction mixture may be slowly
raised from room temperature (e.g., 20° C.) to about 200°
C., the reaction mixture may be maintained at ambient pressure (e.g.,
about 1 atmosphere) or, for volatile diamines, greater than ambient
pressure, or a combination thereof. The product may be isolated, for
instance by filtration when a solid or evaporation of starting materials
at a readily ascertainable combination of temperature and pressure when a
liquid, or may be used in the polymerization reaction without isolation,
as discussed below.

[0054]Various processes may be used for preparing polyesteramides of
formula (I). In one preferred process, the formula (A) monomer product is
synthesized and isolated as described above (but not purified), and then
copolymerized with a diacid or diester of formula (C) and a diol of
formula (D):

HO--R--OH formula (D)

Typically, the polymerization is carried out in the presence of one of the
many known polyester catalysts, such as titanium (IV) butoxide and at
elevated temperature (for example, about 165 to 250° C.) with
reduced pressure applied as needed to facilitate molecular weight
increase. Various mole ratios of reactants can be used. For example, a
mole ratio of formula (A) monomer to diacid or diester of about 1:0.1 to
about 1:50, preferably between 1:1 and 1:20, and a mole ratio of formula
(A) monomer to diol of about 1:1.1 to about 1:100, preferably about 1:2
to about 1:50, are preferred. For another aspect wherein the invention
provides a copolyesteramide of formula (I) as defined above, preferred is
a mole ratio of formula (A) monomer to diacid or diester of about 1:0.1
to 1:0. When x is 0, the mole ratio of formula (A) monomer to diacid or
diester of 1:0, i.e., diacid or diester is absent. The reaction is
continued until sufficient quantities of polymer of desired molecular
weight are formed, for instance about 0.1-24 hours. The pressure in the
reaction may be reduced to facilitate removal of volatile components. The
temperature of the reaction may then be lowered to room temperature and
the product polymer removed from the reaction vessel or polymer can be
removed from the reactor while molten with temperature increased as
needed.

[0055]In another preferred process for synthesizing polymer of formula
(I), this process referred to herein as the "in-situ" process, the
formula (A) monomer is prepared as described above, but is not isolated
from its reaction mixture. Rather, the reaction mixture containing the
formula (A) monomer is copolymerized with formula (C) and formula (D)
monomers. Similar reaction conditions to those described earlier may be
used.

[0056]In a further preferred process for synthesizing polymer of formula
(I), referred to herein as the "one-pot" or "direct" method, all the
materials used for synthesizing monomer and polymer (the diamine of
formula (B), the diacid or diester of formula (C) and the diol of formula
(D)) are reacted together in a single vessel. Again the reaction is
preferably conducted in the presence of catalyst, such as titanium (IV)
butoxide. Additional catalyst(s) may be added at almost any point in the
"direct" method.

[0057]The formula (I) copolyesteramides of this invention are not intended
to be limited by molecular weight. It is preferred, however, that the
copolyesteramides be at least about 2000 grams per mole (g/mol) in number
average molecular weight (Mn) and less than about 100,000 g/mol and
it is more preferred that the molecular weight Mn be between about
4000 g/mol and about 50,000 g/mol.

[0058]In the preparation of the materials of the invention it is possible
to control the copolyesteramides molecular weight Mn by
off-stoichiometry of the monomers utilized in preparing the product or
the utilization of a terminating agent such as a monoacid, monoester,
monol, monoamine, and other single functional reactive species added at
any point during the polymerization. It is also possible to prepare a
branched material by adding a reactive trifunctional species, or higher
polyfunctional species, at some point in the polymerization process with
examples of such trifunctional species including, but not limited to,
triacids, trimesters, triols, triamines, and other reactive
polyfunctional species.

[0059]As demonstrated by the Examples below, the polymer of formula (I)
prepared according to the invention exhibits superior physical
properties, when compared to polymer prepared by known methods

[0061]A "heteroaliphatic" group is an aliphatic group that contains one or
more non-carbon atoms in the hydrocarbon chain of the aliphatic group
(e.g., one or more non-neighboring CH2 groups are replaced with O, S
or NH). Preferred heteroaliphatic groups include C2-C12
heteroalkylenes, more preferably C2-C8 heteroalkylenes, and
particularly where the one or more non-carbon atoms are oxygen.

[0062]A "cycloalkyl" group refers to a saturated carbocyclic radical
having three to twelve carbon atoms, preferably three to seven. The
cycloalkyl can be monocyclic, or a polycyclic fused system. Examples of
such radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl
and cycloheptyl. The cycloalkyl groups herein are optionally substituted
in one or more substitutable positions with various groups. For example,
such cycloalkyl groups may be optionally substituted with, among others,
one or more, preferably 6 or less, halides, alkoxy groups, hydroxy
groups, thiol groups, carboxylic ester groups, ketone groups, carboxylic
acid groups, amines, and carboxamides as described above for substituents
of aliphatic groups. A "cycloalkylene" is a diradical but otherwise is as
defined for cycloalkyl.

[0063]"-Alkylene-cycloalkyl-, "-alkylene-cycloalkyl-alkylene-,"
"-heteroalkylene-cycloalkyl-,"
"-heteroalkylene-cycloalkyl-heteroalkylene-," refer to various
combinations of alkyl, heteroalkyl, and cycloalkyl, and include groups
such as oxydialkylenes (e.g., diethylene glycol), groups derived from
branched diols such as neopentyl glycol or derived from cycloaliphatic
diols such as Dow's UNOXOL® (Union Carbide Chemicals & Plastics
Technology Corporation of The Dow Chemical Company) which is an isomer
mixture of 1,3- and 1,4-cyclohexanedimethanol, and other non-limiting
groups, such -methylcyclohexyl-, -methyl-cyclohexyl-methyl-, and the
like.

[0064]By "heterocycloalkyl" or "heterocycle" is meant one or more
carbocyclic ring systems of 4-, 5-, 6-, or 7-membered rings, which
includes fused ring systems of 9-11 atoms, containing at least one and up
to four heteroatoms (preferably non-adjacent) selected from nitrogen,
oxygen, or sulfur. Preferred heterocycles contain two nitrogen atoms in
the ring, such as piperazinyl. The heterocycloalkyl groups herein are
optionally substituted in one or more substitutable positions with
various groups. For example, such heterocycloalkyl groups may be
optionally substituted with, among others, one or more, preferably 6 or
less, halides, alkoxy groups, hydroxy groups, thiol groups, carboxylic
ester groups, ketone groups, carboxylic acid groups, amines, and
carboxamides as described above for substituents of aliphatic groups. A
"heterocycloalkylene" is a diradical group but otherwise is as defined
for heterocycloalkyl.

[0065]By "polyalkylene oxide" (e.g., in the definition of variable group
"R") is meant a diradical at two different carbon atoms of an
-alkylene-(O-alkylene)m-segment, wherein each m independently is an
integer of 1 or higher, including polyalkylene oxides containing mixed
length alkylenes. Examples of polyalkylene oxides are polytetramethylene
ethers (i.e. R is
--CH2CH2CH2CH2--(OCH2CH2CH2CH2).s-
ub.m--), polypropylene oxides (i.e. R is
--CH2CH(CH3)--[OCH2CH(CH3)]m--), and
polyethylene oxides (i.e. R is
--CH2CH2--(OCH2CH2)m--).

[0066]Unless stated otherwise, all variables (e.g., x, y, n, R, and the
like) are independently selected. Variables x and y may be selected such
that a number average molecular weight Mn of from about 2000 g/mol
to less than about 100,00 g/mol, or a preferred Mn therein, of a
compound of formula (I) is obtained.

[0067]The following examples are illustrative of the invention but are not
intended to limit its scope.

EXAMPLES

General

[0068]Proton NMRs are performed on a Bruker 250 MHz spectrometer on
typical 1-10 wt % solutions typically in d4-acetic acid. Proton NMR is
used to determine monomer purity, copolymer composition, and copolymer
number average molecular weight Mn utilizing the CH2OH end
groups. Proton NMR assignments are dependent on the specific structure
being analyzed as well as the solvent, concentration, and temperatures
utilized for measurement. For ester amide monomers and copolyesteramides,
d4-acetic acid is a convenient solvent. For ester amide monomers of the
type called A2A, A4A, and A6A that are methyl esters typical peak
assignments are about 3.6-3.7 ppm for C(═O)--OCH3; about 3.2-3.3
ppm for N--CH2--; about 2.2-2.4 ppm for C(═O)--CH2--; and
about 1.2-1.7 ppm for C--CH2--C. For copolyesteramides that are
based on A2A, A4A, and A6A with 1,4-butanediol, typical peak assignments
are about 4.1-4.2 ppm for C(═O)--OCH2--; about 3.2-3.4 ppm for
N--CH2--; about 2.2-2.5 ppm for C(═O)--CH2--; about 1.2-1.8
ppm for C--CH2--C, and about 3.6-3.75 --CH2OH end groups.

[0069]Differential scanning calorimetry (DSC) is done with a TA Instrument
2920 or Q100 typically with heating rates and cooling rates of 10°
C./min. By DSC, the glass transition temperature, Tg, is taken as the
temperature in ° C. at the half-height of the glass transition on
the second heating of the sample. (e.g. reheat or rescan). By DSC, the
melting point temperature, Tm, is the temperature in ° C. at the
maxima(s) (e.g. peak(s)) of the endothermic melting transition(s) on the
second heating of the sample (e.g. reheat or rescan). By DSC, the
crystallization temperature, Tcr, is the temperature in ° C. at
the maxima(s) (e.g. peak(s)) of the exothermic crystallization
transition(s) upon cooling from the melt. By DSC, the heat of fusion,
ΔHf, is the integrated peak area, expressed in Joules per gram
(J/g), of the melting peak(s) on the second heating of the sample (e.g.
reheat or rescan). By DSC, the heat of crystallization, ΔHcr, is
the integrated peak area, expressed in J/g, of the crystallization
peak(s) upon cooling from the melt. Inherent viscosities are measured on
about 0.5 grams per deciliter (g/dL) solutions at 30° C. in an
appropriate solvent such as chloroform/methanol(1/1),
phenol/1,1,2,2-tetrachlorethane(3/2), or m-cresol. Tensile testing is
performed according to ASTM 1708 using microtensile specimen geometry on
an Instron 5581. Dynamic mechanical spectroscopy (DMS) is performed in
tensile mode on a TA Instruments RSI solid state rheometer at a typical
frequency of 1 Hz and over a typical temperature range starting from
-130° C. until no more than about 230° C.

[0070]To determine the weight % water uptake after 24 hours exposure ("24
Hr H2O Wt %" in Table 2), molded discs that are approximately 10 mm in
diameter and approximately 0.4 mm thick are dried for 48 hours in a
50° C. vacuum oven. The discs are immediately weighed (weight at
t0 hrs) and then immersed in approximately 2 milliliters (mL) of
deionized water at room temperature. After 24 hours of immersion, discs
are removed from water and patted dry with paper towels and immediately
weighed (weight at t24 hrs). 24 Hr H2O Wt %=[(weight at t24
hrs-weight at t0 hrs)/weight at t0 hrs] 100%.

Example 1

Preparation of Diamide Diester Monomer ("A2A")

##STR00006##

[0072]In a nitrogen atmosphere, titanium (IV) butoxide (0.92 g, 2.7 mmol),
ethylene diamine (15.75 g, 0.262 mol), and dimethyl adipate (453.7 g,
2.604 mol) are loaded into a 3-neck, 1 L round bottom flask that is
stoppered and transferred to hood. Flask is placed under positive
nitrogen via inlet adaptor attached to a Firestone valve. Stir-shaft with
blade is inserted into flask along with stir bearing with overhead stir
motor. Stoppered condenser is inserted into flask. A thermocouple
inserted thru septa is also inserted into the flask. Flask is warmed with
a hemisphere heating mantle that is attached to proportional temperature
controller. Basic reaction profile is 2.0 hours to/at 50° C.; 2.0
hours to/at 60° C.; 2.0 hours to/at 80° C.; overnight at
100° C. Flask is slowly cooled with stirring to about 50°
C., stirring stopped and cooled to room temperature. Approximately 200 mL
of cyclohexane is add to the reaction flask with agitation for a
filterable slurry with solid collected on a medium porosity glass
filtration funnel to facilitate removal of unreacted dimethyl adipate.
Collected solids are washed twice with about 50 mL of cyclohexane.
Product is dried overnight in an about 50° C. vacuum oven. Dried
product is broken up and re-slurried in fresh cyclohexane (about 300 mL),
recollected by filtration, rinsed twice with about 50 mL cyclohexane, and
dried to constant weight in a 50° C. vacuum oven under full pump
vacuum. Yield=59.8 grams (66%). Proton NMR in d4-acetic acid generates an
Hw of 1.13. A product such as this is designated as crude monomer.

[0073]Purification of "A2A". Crude A2A monomer (35.0 grams) is heated to a
boil with stirring in the presence of chloroform (about 150 mL) and
methanol (about 285 mL) with the hot mixture filtered to remove insoluble
materials. The solvents from the filtrate are removed on a rotary
evaporator under reduced pressure with isolated monomer dried to constant
weight in a 50° C. vacuum oven for a recovery of 34 grams product
that is soluble in a mixture of chloroform/methanol. This soluble product
is recrystallized from about 390 mL of methanol with a dried recovered
yield of 16.8 grams. Proton NMR in d4-acetic acid generates a Hw, of
1.033. This monomer is typically designated as purified (P).

Example 2

Preparation of Diamide Diester Monomer ("A4A")

##STR00007##

[0075]In a nitrogen atmosphere, 1,4-diaminobutane (23.1 g, 0.262 mol), and
dimethyl adipate (453.7 g, 2.604 mol) are loaded into a 3-neck, 1 L round
bottom flask that is stoppered and transferred to hood. Flask is placed
under gentle nitrogen purge via inlet adaptor and exits adaptor attached
to bubbler. Stir-shaft with blade is inserted into flask along with stir
bearing with overhead stir motor. Dean-Stark trap and condenser are
inserted into flask. A thermocouple inserted thru septa is also inserted
into the flask. Flask is warmed with a hemisphere heating mantle that is
attached to proportional temperature controller. Basic reaction profile
is warm to 50° C. and inject titanium (IV) butoxide (0.93 mL, 2.7
mmol); about 30 minutes to/at 60° C.; about 20 minutes to/at
75° C.; about 45 minutes to/at 100° C.; about 90 minutes
to/at 125° C.; and about 3.5 hours to/at 150° C. Flask is
cooled with stirring to about 75° C. and approximately 100 mL of
tetrahydrofuran is added to the reaction flask with agitation for a
filterable slurry upon cooling with solid collected on a Buchner funnel
to facilitate removal of unreacted dimethyl adipate. Collected solids are
washed four times with about 25-50 mL of tetrahydrofuran. Product is
dried overnight in an about 50° C. vacuum oven. Dried product is
broken up and re-slurried in fresh tetrahydrofuran (about 300 mL),
recollected by filtration, rinsed twice with about 50 mL tetrahydrofuran,
and dried to constant weight in a 95° C. vacuum oven under full
pump vacuum. Yield=74.4 grams. Proton NMR in d4-acetic acid generates an
Hw of 1.1625. A product such as this is designated as crude monomer.

[0076]Purification of "A4A". Crude A4A monomer (75 grams) is heated to a
boil with stirring in the presence of chloroform (about 525 mL) with the
hot mixture filtered to remove insoluble materials. The solvents from the
filtrate are removed on a rotary evaporator under reduced pressure with
isolated monomer dried to constant weight in a 60° C. vacuum oven
for a recovery of 52 grams product that is soluble in chloroform. Proton
NMR in d4-acetic acid generates a Hw of 1.026. This monomer is
typically designated as purified (P).

Example 3

Preparation of Diamide Diester Monomer ("A6A")

##STR00008##

[0078]In a nitrogen atmosphere, 1,6-diaminohexane (30.45 g, 0.262 mol),
and dimethyl adipate (453.7 g, 2.604 mol) are loaded into a 3-neck, 1 L
round bottom flask that is stoppered and transferred to hood. Flask is
placed under gentle nitrogen purge via inlet adaptor and exits adaptor
attached to bubbler. Stir-shaft with blade is inserted into flask along
with stir bearing with overhead stir motor. Dean-Stark trap and condenser
are inserted into flask. A thermocouple inserted thru septa is also
inserted into the flask. Flask is warmed with a hemisphere heating mantle
that is attached to proportional temperature controller. Basic reaction
profile is warm to 50° C. and inject titanium (IV) butoxide (0.93
mL, 2.7 mmol); about 45 minutes to/at 60° C.; about 20 minutes
to/at 75° C.; about 45 minutes to/at 100° C.; about 120
minutes to/at 125° C.; and about 3.5 hours to/at 150° C.
Flask is cooled with stirring to about 75° C. and approximately
100 mL of tetrahydrofuran is added to the reaction flask with agitation
for a filterable slurry upon cooling with solid collected on a Buchner
funnel to facilitate removal of unreacted dimethyl adipate. Collected
solids are washed several times with about 50-100 mL of tetrahydrofuran.
Product is dried to constant weight in an about 50° C. vacuum
oven. Yield=81.2 grams. Proton NMR in d4-acetic acid generates an Hw of
1.137. A product such as this is designated as crude monomer.

[0079]Purification of "A6A". Crude A6A monomer (38 grams) is heated to a
boil with stirring in the presence of chloroform (about 370 mL) with the
hot mixture filtered to remove insoluble materials. The solvents from the
filtrate are removed on a rotary evaporator under reduced pressure with
isolated monomer dried to constant weight in a 50° C. vacuum oven
for a recovery of 27 grams product that is soluble in chloroform. Proton
NMR in d4-acetic acid generates a Hw, of 1.026. This monomer is
typically designated as purified (P).

Example 4

Monomer Purity

[0080]As described above, the purity of monomers of formula (A) can be
determined by 1H NMR spectroscopy. Table 1 below provides
comparisons between pure monomers (Hw no more than 1.05) and non-pure
monomers according to the invention. Hw are determined as described
above.

[0081]Into a 250 mL round bottom flask is loaded titanium (IV) butoxide
(0.123 g, 0.361 mmol), purified
dimethyl-7,12-diaza-6,13-dioxo-1,18-octadecanedioate (A4A, 22.36 g, 60.05
mmol), dimethyl adipate (31.38 g, 0.1801 mol) and 1,4-butanediol (43.29
g, 0.480 mol). Into the flask is inserted a stir-shaft and blade,
bearing, along with a Vigoreaux column/distillation head. Apparatus is
degassed with three vacuum/N2 cycles before being left under
N2. Column is heat traced and flask is immersed into bath at
160° C. Set point of bath is increased to 175° C. with a
total of 2 hours to/at 175° C. under positive N2. Over a
period of about 2.5 hours, pressure is lowered stepwise and held at 10
Torr. Apparatus is placed under full vacuum of about 0.4 Torr for 2 hours
at bath temperature of 175° C. Apparatus is kept under full vacuum
of about 0.4 Torr for a total of about 3 hours while the bath temperature
is increased and held at 190° C. The product inherent
viscosity=0.372 dL/g (0.5 g/dL, 30.0° C., chloroform/methanol
(1/1, w/w)). DSC, Tensile, and Dynamic Mechanical characterizations are
found in FIGS. 1-4.

[0086]Into a 250 mL round bottom flask is loaded titanium (IV) butoxide
(0.123 g, 0.361 mmol), crude dimethyl
7,12-diaza-6,13-dioxo-1,18-octadecanedioate (A4A, 22.36 g, 60.05 mmol),
dimethyl adipate (31.38 g, 0.1801 mol) and 1,4-butanediol (43.29 g. 0.480
mol). Into the flask is inserted a stir-shaft and blade, bearing, along
with a Vigoreaux column/distillation head. Apparatus is degassed with
three vacuum/N2 cycles before being left under N2. Column is
heat traced and flask is immersed into bath at 160° C. Set point
of bath is increased to 175° C. with a total of 2 hours from 160
to 175° C. under positive N2. Over a period of about 2.6
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
placed under full vacuum of about 0.4 Torr for 2 hours at bath
temperature of 175° C. Apparatus is kept under full vacuum of
about 0.3 Torr for a total of about 7 hours and the bath temperature is
increased and held at 190° C. Product Inherent Viscosity=0.395
dL/g (0.5 g/dL, 30.0° C., chloroform/methanol (1/1, w/w)). DSC,
Tensile, and Dynamic Mechanical characterizations are found in FIGS. 1-4.

Example 7

Polymerization Using an In-Situ Process with Diester Diamide A4A Monomer

[0087]Into a 2-neck 250 mL round bottom flask are loaded titanium (IV)
butoxide (0.341 g, 1.0 mmol), 1,4-diaminobutane (8.824 g, 0.1001 mol),
and dimethyl adipate (87.16 g, 0.5004 mol). First stage reaction
apparatus is completed with N2 inlet adaptor, stir-shaft & blade,
bearing, Claisen adaptor, Dean-Stark trap, condenser, outlet adaptor, and
temperature controlled heating mantle. Reaction profile for first stage
is 10 minutes to/at 50° C., 15 minutes to/at 60° C., 30
minutes to/at 75° C., 60 minutes to/at 100° C., 135 minutes
to/at 125° C., and 150 minutes to/at 150° C. Reaction
mixture is cooled with all but stir-shaft and blade removed from the
apparatus and a Vigoreaux column/distillation head with bearing is
inserted into the flask along with the 2nd neck stoppered.
1,4-Butanediol (71 mL, 0.80 mol) and titanium (IV) butoxide (0.15 mL,
0.44 mmol) are injected into the flask. Apparatus is degassed with three
vacuum/N2 cycles before being left under N2. Column is heat
traced and flask is immersed into bath at 160° C. Set point of
bath is increased to 175° C. with a total of 2 hours to/at
175° C. under positive N2. Over a period of about 2.5 hours,
pressure is lowered stepwise and held at 10 Torr. Apparatus is placed
under full vacuum of about 0.4 Torr for 2 hours at bath temperature of
175° C. Apparatus is kept under full vacuum of about 0.4 Torr for
a total of about 5 hours with bath temperature increased and held at
190° C. Product Inherent Viscosity=0.316 dL/g (0.5 g/dL,
30.0° C., chloroform/methanol (1/1, w/w)). DSC, Tensile, and
Dynamic Mechanical characterizations are found in FIGS. 1-4.

[0088]Into a 250 mL round bottom flask is loaded tin octanoate (0.159 g,
0.392 mmol), crude dimethyl 7,12-diaza-6,13-dioxo-1,18-octadecanedioate
(A4A, 24.00 g, 64.44 mmol), dimethyl adipate (33.67 g, 0.1933 mol),
UNOXOL® (18.59 g, 0.1288 mol, a mixture of 1,3- and
1,4-cylclohexanedimethanol) and 1,4-butanediol (34.85 g. 0.3867 mol).
Into the flask is inserted a stir-shaft and blade, bearing, along with a
Vigoreaux column/distillation head. Apparatus is degassed with three
vacuum/N2 cycles before being left under N2. Column is heat
traced and flask is immersed into bath at 160° C. Set point of
bath is increased to 175° C. with a total of 2 hours from 160 to
175° C. under positive N2. Over a period of about 2.3 hours,
pressure is lowered stepwise and held at 10 Torr. Apparatus is placed
under full vacuum of about 0.4 Torr for 2 hours at bath temperature of
175° C. Apparatus is kept under full vacuum of about 0.3 Torr for
about 2 hours with bath temperature is increased and held at 190°
C. Apparatus is kept under full vacuum of about 0.3 Torr for about 2
hours with bath temperature is increased and held at 210° C.
Product Inherent Viscosity=0.293 dL/g (0.5 g/dL, 30.0° C.,
chloroform/methanol (1/1, w/w)). By 1H-NMR, about 29 mol % of repeat
units contain A4A amide with product having a Mn of 13,400. By
tensile testing, strain @ break=320%; modulus, tan 0.15%=119 megaPascals
(MPa); tensile stress @ max load=6.2 MPa; integrated stress-strain=6.03
inch-pound force (in-lbf).

Example 9

Polymerization Using Crude Diester Diamide A4A Monomer with Mixture of
Diol and Polyol

[0089]Into a 250 mL round bottom flask is loaded titanium (IV) butoxide
(0.078 g, 0.23 mmol), crude dimethyl
7,12-diaza-6,13-dioxo-1,18-octadecanedioate (A4A, 13.97 g, 37.50 mmol),
dimethyl adipate (19.60 g, 0.1125 mol), polytetramethylene ether glycol,
Mn 983 (36.86 g, 37.50 mmol, TERATHANE® 1000) and 1,4-butanediol
(23.66 g. 0.2625 mol). Into the flask is inserted a stir-shaft and blade,
bearing, along with a Vigoreaux column/distillation head. Apparatus is
degassed with three vacuum/N2 cycles before being left under
N2. Column is heat traced and flask is immersed into bath at
160° C. Set point of bath is increased to 175° C. with a
total of 2 hours from 160 to 175° C. under positive N2. Over
a period of about 2.5 hours, pressure is lowered stepwise and held at 10
Torr. Apparatus is placed under full vacuum of about 0.3 Torr for 2 hours
at bath temperature of 175° C. Apparatus is kept under full vacuum
of about 0.4 Torr for about 2 hours with bath temperature is increased
and held at 190° C. Apparatus is kept under full vacuum of about
0.4 Torr for about 2 hours with bath temperature is increased and held at
210° C. Product Inherent Viscosity=0.485 dL/g (0.5 g/dL,
30.0° C., chloroform/methanol (1/1, w/w)). By 1H-NMR, about
34 mol % of repeat units contain A4A amide. By tensile testing, strain @
break=317%; modulus, tan 0.15%=4.4 MPa; tensile stress @ max load=3.1
MPa; integrated stress-strain=3.17 in-lbf.

Example 10

Polymerization Using Crude Diester Diamide A4A Monomer with Mixture of
Diol and Polyol

[0090]Into a 250 mL round bottom flask is loaded titanium (IV) butoxide
(0.084 g, 0.25 mmol), crude dimethyl
7,12-diaza-6,13-dioxo-1,18-octadecanedioate (A4A, 29.77 g, 79.93 mmol),
dimethyl adipate (13.92 g, 79.91 mmol), poly(ethylene
glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), about
10 wt % PEG, Mn 1100 (22.65 g, 20.59 mmol) and 1,4-butanediol (26.95
g. 0.2990 mol). Into the flask is inserted a stir-shaft and blade,
bearing, along with a Vigoreaux column/distillation head. Apparatus is
degassed with three vacuum/N2 cycles before being left under
N2. Column is heat traced and flask is immersed into bath at
160° C. Set point of bath is increased to 175° C. with a
total of 2 hours from 160 to 175° C. under positive N2. Over
a period of about 2.5 hours, pressure is lowered stepwise and held at 10
Torr. Apparatus is placed under full vacuum of about 0.4 Torr for 2 hours
at bath temperature of 175° C. Apparatus is kept under full vacuum
of about 0.4 Torr for about 2 hours with bath temperature is increased
and held at 190° C. Apparatus is kept under full vacuum of about
0.4 Torr for about 2 hours with bath temperature is increased and held at
210° C. Product Inherent Viscosity=0.386 dL/g (0.5 g/dL,
30.0° C., chloroform/methanol (1/1, w/w)). By 1H-NMR, about
62 mol % of repeat units contain A4A amide. By tensile testing, strain @
break=558%; modulus, tan 0.15%=68 MPa; tensile stress @ max load=12.2
MPa; integrated stress-strain=14.35 in-lbf.

Example 11

Property Measurements of Various Polyesteramides

[0091]Table 2 below provides physical properties of various polyesteramide
polymers prepared from decreased perfection diamide diester monomers
according to the invention, compared with polymers prepared from purified
diamide diester monomers. The following abbreviations are used in Table
2: [0092]Hard segment=monomer of formula (A) utilized in preparing
copolymer where A represents R''=four methylenes, and the number 2, 4, or
6 represents the number of methylene groups between the amine groups in
formula (B) structures. [0093]Mole %=amount of monomer of formula (A)
incorporated into copolymer assuming for measurement purposes that n=1
using proton NMR [0094]PBA=polybutylene adipade (product of dimethyl
adipate and 1,4-butanediol) [0095]C=polymerization using crude monomer,
such as described in Example 6 [0096]P=polymerization using purified
monomer, such as described in Example 5 [0097]I=polymerization using in
situ procedure, such as described in Example 7 [0098]IV=inherent
viscosity [0099]Mn=number average molecular weight, in thousands of
g/mol (K) from proton NMR; obtained from integrated ratio of
C(O)--CH2/CH2OH and multiplying by the average molecular weight
of a polymer repeat unit [0100]Tm=melting point maxima in DSC at
10° C./min heating rate upon rescan [0101]ΔHf=heat of
fusion; integration of melting peak at 10° C./min upon rescan in
DSC [0102]Tcr=crystallization temperature maxima in DSC at 10°
C./min cooling rate from melt [0103]ΔHcr=heat of crystallization;
integration of crystallization peak at 10° C./min cooling rate
from melt

[0104]The data reveal that polymer products with decreased perfection do
not completely melt until some temperature greater than when a purified
monomer is utilized as illustrated in the DSC in FIG. 1 and that the
materials with decreased perfection also crystallize at a higher
temperature than when a purified monomer is utilized as illustrated in
FIG. 2. Retaining crystallinity to a higher temperature allows a material
to be used at higher temperatures due to improved dimensional stability
which is illustrated in FIG. 4 where the products from a crude process or
in-situ process have a higher modulus at higher temperatures above about
70° C. Crystallizing at a higher temperature in materials with
decreased perfection can offer the advantage of fabricated articles that
solidify at a higher temperature which can offer productivity.

Example 12

[0105]Homopolyesteramide (x=0) from Crude A2A and 1,4-Butanediol. In a
nitrogen atmosphere, titanium (IV) butoxide (0.038 g, 0.11 mmol), crude
A2A (23.24 g, 67.49 mmol), and 1,4-butanediol (12.16 g, 0.1350 mol) are
loaded into a 100 mL round bottom flask. Into the flask is inserted a
stir-shaft and blade, take-off adaptor, and stir-bearing. Apparatus is
degassed with three vacuum/nitrogen cycles before being left under
nitrogen. Adaptor is heat-traced and flask is immersed into 160°
C. bath with bath set point raised to 175° C. with a total of 2
hours from 160° C. to 175° C. Over a period of about 2
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
kept under full vacuum (about 0.7 Torr) for a total of about 3.5 hours
and the bath temperature is increased and held at 190° C. Product
inherent viscosity=0.397 dL/g (0.5 g/dL, 30.0° C., m-cresol). By
DSC, Tg=-67° C., Tm=150, 163° C. (42 J/g),
Tcr=130° C. (37 J/g).

Example 13

[0106]Homopolyesteramide (x=0) from Crude A4A and 1,4-Butanediol. In a
nitrogen atmosphere, titanium (IV) butoxide (0.035 g, 0.10 mmol), crude
A4A (23.37 g, 62.74 mmol), and 1,4-butanediol (11.31 g, 0.1255 mol) are
loaded into a 100 mL round bottom flask. Into the flask is inserted a
stir-shaft and blade, take-off adaptor, and stir-bearing. Apparatus is
degassed with three vacuum/nitrogen cycles before being left under
nitrogen. Adaptor is heat-traced and flask is immersed into 160°
C. bath with bath set point raised to 175° C. with a total of 2
hours from 160° C. to 175° C. Over a period of about 2
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
kept under full vacuum (about 0.35 Torr) for a total of about 2 hours and
the bath temperature is increased and held at 190° C. Product
inherent viscosity=0.421 dL/g (0.5 g/dL, 30.0° C., m-cresol). By
DSC, Tg=-51° C., Tm=143, 157° C. (47 J/g),
Tcr=111° C. (39 J/g).

Example 14

[0107]Homopolyesteramide (x=0) from Crude A4A and 1,3-Propanediol. In a
nitrogen atmosphere, titanium (IV) butoxide (0.036 g, 0.10 mmol), crude
A4A (24.22 g, 65.02 mmol), and 1,3-propanediol (9.90 g, 0.13 mol) are
loaded into a 100 mL round bottom flask. Into the flask is inserted a
stir-shaft and blade, take-off adaptor, and stir-bearing. Apparatus is
degassed with three vacuum/nitrogen cycles before being left under
nitrogen. Adaptor is heat-traced and flask is immersed into 160°
C. bath with bath set point raised to 175° C. with a total of 2
hours from 160° C. to 175° C. Over a period of about 2
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
kept under full vacuum (about 0.25 Torr) for a total of about 3 hours and
the bath temperature is increased stepwise and finally held at
210° C. Product inherent viscosity=0.417 dL/g (0.5 g/dL,
30.0° C., m-cresol). By DSC, Tg=-64° C.,
Tm=153° C. (78 J/g), Tcr=128° C. (61 J/g).

Example 15

[0108]Homopolyesteramide (x=0) from Crude A6A and 1,4-Butanediol. In a
nitrogen atmosphere, titanium (IV) butoxide (0.033 g, 0.096 mmol), crude
A6A (23.47 g, 58.61 mmol), and 1,4-butanediol (10.56 g, 0.1172 mol) are
loaded into a 100 mL round bottom flask. Into the flask is inserted a
stir-shaft and blade, take-off adaptor, and stir-bearing. Apparatus is
degassed with three vacuum/nitrogen cycles before being left under
nitrogen. Adaptor is heat-traced and flask is immersed into 160°
C. bath with bath set point raised to 175° C. with a total of 2
hours from 160° C. to 175° C. Over a period of about 2
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
kept under full vacuum (about 0.3 Torr) for a total of about 5.5 hours
and the bath temperature is increased stepwise and held at 210° C.
Product inherent viscosity=0.170 dL/g (0.5 g/dL, 30.0° C.,
m-cresol). By DSC, Tg=-65° C., Tm=131, 142° C.
(60 J/g), Tcr=114° C. (50 J/g).

Example 16

[0109]Homopolyesteramide (x=0) from Crude A4A and 1,3-Propanediol. In a
nitrogen atmosphere, titanium (IV) butoxide (0.034 g, 0.10 mmol), crude
A4A (24.27 g, 60.60 mmol), and 1,3-propanediol (9.22 g, 0.121 mol) are
loaded into a 100 mL round bottom flask. Into the flask is inserted a
stir-shaft and blade, take-off adaptor, and stir-bearing. Apparatus is
degassed with three vacuum/nitrogen cycles before being left under
nitrogen. Adaptor is heat-traced and flask is immersed into 160°
C. bath with bath set point raised to 175° C. with a total of 2
hours from 160° C. to 175° C. Over a period of about 2
hours, pressure is lowered stepwise and held at 10 Torr. Apparatus is
kept under full vacuum (about 0.3 Torr) for a total of about 4 hours and
the bath temperature is increased stepwise and finally held at
210° C. Product inherent viscosity=0.756 dL/g (0.5 g/dL,
30.0° C., m-cresol). By DSC, Tg=-62° C.,
Tm=149° C. (69 J/g), Tcr=128° C. (57 J/g).

[0110]The examples illustrate simpler and more economical processes for
preparing polyesteramides and new polyesteramides that exhibit improved
physical properties.

[0111]While the invention has been described above according to its
preferred embodiments, it can be modified within the spirit and scope of
this disclosure. This application is therefore intended to cover any
variations, uses, or adaptations of the invention using the general
principles disclosed herein. Further, the application is intended to
cover such departures from the present disclosure as come within the
known or customary practice in the art to which this invention pertains
and which fall within the limits of the following claims.